CN102471441B - Method for producing polyols on the basis of renewable resources - Google Patents

Method for producing polyols on the basis of renewable resources Download PDF

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CN102471441B
CN102471441B CN201080030700.5A CN201080030700A CN102471441B CN 102471441 B CN102471441 B CN 102471441B CN 201080030700 A CN201080030700 A CN 201080030700A CN 102471441 B CN102471441 B CN 102471441B
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oil
acid
polyvalent alcohol
catalyzer
fat
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CN102471441A (en
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A·昆斯特
M·舍伯尔
J·H·特莱斯
B·埃林
J·罗伊贝尔
G-D·特本
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/36—Hydroxylated esters of higher fatty acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/18—Polyhydroxylic acyclic alcohols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid

Abstract

The invention relates to a method for producing polyols, comprising the following steps: a) reacting unsaturated natural fats, unsaturated natural fatty acids and/or fatty acid esters with dinitrogen monoxide, and b) reacting the product obtained in step a) with hydrogen using a heterogeneous catalyst.

Description

The method for preparing polyvalent alcohol on basis, renewable source
The present invention relates to a kind of method for preparing polyvalent alcohol on the basis of natural oil, polyvalent alcohol is more specifically for the preparation of urethane.
Urethane is for many technical fields.They usually by polyisocyanates with there are at least two compounds to the hydrogen atom of responding property of isocyanate groups react acquisition under the existence of whipping agent and optional catalyst and conventional auxiliary agent and/or auxiliary reagent.
Recently, the importance of the urethane starting ingredient based on renewable raw material increases day by day.More specifically in the situation that there are at least two compounds to the hydrogen atom of responding property of isocyanate groups, can use natural oil & fat, they carried out chemical modification usually before for the urethane application, thereby introduced at least two hydrogen atoms to responding property of isocyanate groups.Generally speaking, during chemical modification, natural oil and/or fat are hydroxy-functionals, and optionally modification in one or more other steps.In the PU system, use the fat derivant of hydroxy-functional and/or the example of oily derivative to comprise for example WO2006/116456 and WO2007/130524.
Hydrogen atoms for polyurethane industrial must be incorporated in most of natural oil by chemical process as mentioned above.For this reason, according to prior art, the method adopted is to utilize the two keys that occur in the fatty acid ester of many oil basically.At first, fat can be oxidized to corresponding fat epoxide or lipid acid epoxide by reacting under the existence of catalyzer with percarboxylic acids.Subsequently, the ring-opening reaction that oxirane ring carries out acid catalysis or base catalysis under alcohol, water, carboxylic acid, halogen or hydrogen halide exist, thereby fat or the fat derivant of formation hydroxy-functional, respectively referring to for example WO2007/127379 and US2008076901.The shortcoming of this method is the material that first reactions steps (epoxidation) needs to use high corrosion resistance, and this reactions steps is at industrial use corrodibility peroxyformic acid or use peracetic acid to carry out.In addition, after producing, for economic reasons and must be by distillation concentrated and recirculation again, and this makes and must use the water distilling apparatus of erosion resistance the rare percarboxylic acids obtained, so be more to consume energy and more expensive.
The possibility that another kind carries out hydroxy-functional is first to use the mixture (synthetic gas) of carbon monoxide and hydrogen to carry out hydroformylation under the existence of the catalyzer that makes unsaturated fatty acids or derivative of fatty acid contain cobalt or contain rhodium in the first reactions steps; then the aldehyde functional group hydrogenation that will introduce by this reactions steps becomes hydroxyl (referring to WO 2006/12344A1 or J.Mol.Cat.A; 2002; 184; 65 and J.Polym.Environm.2002; 10; 49), wherein use suitable catalyzer (for example Raney nickel).But, by this response path, must be noted that first reactions steps is hydroformylation reaction, also need at least to use catalysts and solvents, and, for economically viable production, also must again reclaim them and process or regeneration.
EP1170274A1 has described a kind of method for preparing hydroxyl oil, wherein oxidation unsaturated oil under the existence of atmosphericoxygen.The shortcoming of this method is that obtained degree of functionalization is not high, and this reaction must at high temperature carry out, and causes the decomposed of lipid structure.It is division fat or fat derivant under the existence of ozone that another kind is introduced fatty possibility by hydroxyl-functional, and then reduction forms hydroxyl-fat derivant (referring to Biomacromolecules 2005,6,713; J.Am.Oil Chem.Soc.2005,82,653 and J.Am.Oil Chem.Soc.2007,84,173).This operation also must occur in solvent, and usually carries out at low temperatures (10 ℃ to 0 ℃), also causes higher production cost.In addition, the security feature of this operation need to provide expensive security measures, for example detection and control techniques or fire protection.
At Adv.Synth.Catal.2007, described by laughing gas in 349,1604 fat has been carried out to ketonization.Can use homogeneous catalyst that ketone groups is changed into to hydroxyl.But, do not mention the further processing of these products fully.
A kind of on renewable raw material basis for the preparation of the possibility of the polyvalent alcohol of urethane be make undersaturated natural fat for example soya-bean oil, Trisun Oil R 80, vegetable seed wet goods or corresponding fat derivant for example lipid acid or their monoesters, by corresponding derivatization reaction, obtain respectively fat and the derivative of fatty acid of hydroxy-functional.These materials can be directly used in corresponding PU application, or the basic oxide additional mark is being applied for corresponding PU after on the hydroxy functional group of the fat at hydroxy-functional or fat derivant.Hydroxyl-fat derivant and oxirane react and reaction product can be referring to for example WO2007/143135 and EP1537159 for the example of urethane application.Here, addition reaction is in most of the cases that catalyzer by being called double metal cyanide carries out.
The purpose of this invention is to provide the polyvalent alcohol based on renewable raw material for the urethane application, the polyvalent alcohol based on natural fat and derivative of fatty acid more specifically, they can obtain and cheaply in the situation that choose very simply reaction parameter, can comprise multiple sense, institute is so that product can be used for range of application widely.More particularly, this method can be by simple method in the situation that do not used expensive raw material (catalysts and solvents) to prepare oil & fat.Simultaneously, this method can be removed catalyzer from reaction product in simple mode.
This purpose realizes in the following manner: for example soya-bean oil, Trisun Oil R 80, rapeseed oil, castor-oil plant wet goods or corresponding fat derivant carry out oxidation, fat and the derivative of fatty acid of formation ketonization to make unsaturated natural fat in the first step under the existence of nitrous oxide (also referred to as laughing gas); And in further reactions steps, these products are reduced under the existence of hydrogen and heterogeneous catalyst, obtain hydroxyl-fat.
Therefore, the invention provides a kind of method for preparing the polyvalent alcohol based on renewable raw material, comprise the following steps:
A) unsaturated natural fat, unsaturated natural acid and/or fatty acid ester are reacted with nitrous oxide,
B) product that makes to obtain in a) in step reacts with hydrogen use heterogeneous catalyst.
These materials can directly be used for the application of wide region as polyol component, for example, for corresponding PU application.
Unsaturated natural fat is preferably selected from: Viscotrol C, raisin seed oil, Nigella damascena L. oil, Semen Cucurbitae oil, borage oil, soya-bean oil, Wheat germ oils, rapeseed oil, Trisun Oil R 80, peanut oil, Pericarppium Armeniacae Amarum oil, pistachio oil, Prunus amygdalus oil, sweet oil, Queensland nut oil, Lipoval A, Oleum Hippophae, sesame oil, cannabis oil, hazelnut oil, primrose oil, wild rose oil, Thistle oil, walnut oil, plam oil, fish oil, Oleum Cocois, Yatall MA, maize germ, linseed oil.
Preferred lipid acid and fatty acid ester are to be selected from: tetradecenoic acid, Zoomeric acid, oleic acid, vaccenic acid, petroselinic acid, gadoleic acid, erucic acid, Selacholeic acid, linolic acid, α-and gamma-linolenic acid, therapic acid, arachidonic acid, timnodonic acid, sole acid, and docosahexenoic acid, and their ester.
As fatty acid ester, can not only use whole esterifications but also monohydroxy-alcohol or polyvalent alcohol that use partial esterification.Admissible monohydroxy-alcohol or polyvalent alcohol comprise methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, ethylene glycol, propylene glycol, glycol ether, dipropylene glycol, glycerine, TriMethylolPropane(TMP), tetramethylolmethane, sorbyl alcohol, sucrose and seminose.
Particularly preferably unsaturated natural fat is selected from Viscotrol C, soya-bean oil, plam oil, Trisun Oil R 80 and rapeseed oil.More specifically use soya-bean oil, plam oil, Trisun Oil R 80 and rapeseed oil.These compounds on technical scale at least for the production of biofuel.
Except above-mentioned oil, also can use those oil that obtain from the plant of gene modification, it has different lipid acid and forms.Except described oil, also can use as mentioned above corresponding lipid acid or fatty acid ester.
Reactions steps a) and b) can carry out independently of one another, and optionally also can on when and where, carry out individually.But all three processing steps can carry out by succeedingly.In this respect, also can carry out fully continuously this method.
Step a) is preferably carried out under superatmospheric pressure, more specifically under the pressure of 10-300 bar, carries out; And at high temperature carry out, more specifically carry out at the temperature in 200-350 ℃ of scope., can use the oily or fatty of body or the solution form in suitable solvent here, solvent is for example hexanaphthene, acetone or methyl alcohol.This reaction can be carried out in the stirred reactor of any required design or in tubular reactor; In principle, the reaction in any required other reaction system is possible.Laughing gas used can be used as pure substance or as the mixture be the gas of inertia under reaction conditions, for example nitrogen, helium, argon gas or carbonic acid gas.In this case, the amount of rare gas element is no more than 50 volume %.
For further processing reaction mixture after finishing in reaction, reaction mixture is cooling, where necessary except desolventizing, for example by distillation or extraction, undertaken, and by product in the situation that carry out or be not further processed being supplied to step b).
From step, reaction product a) is at step b) in hydrogenation.This also carries out according to conventional and known method.For this purpose, from step, organic phase and the hydrogen reaction of preferred purification a) preferably carry out under the existence of suitable solvent.For this purpose, organic phase 50-300 bar, more specifically under the pressure of 90-150 bar and 50-250 ℃, more specifically under the existence at hydrogenation catalyst, react at the temperature of 50-120 ℃.Hydrogenation catalyst is heterogeneous catalyst.Preferably use the catalyzer that contains ruthenium.Except ruthenium, catalyzer also can contain other metal, for example the metal of 6-11 family, for example nickel, cobalt, copper, molybdenum, palladium or platinum.
Catalyzer is preferably applied on carrier.Operable carrier is conventional carrier, for example aluminum oxide or zeolite.In a preferred embodiment of the invention, carbon is as solid support material.
Catalyzer can be water-wet.Hydrogenation preferably carries out in fixed bed.
After hydrogenation, remove organic solvent, catalyzer and optional water.Product is purified where necessary.
According to the fat used in a) at processing step or the character of fat derivant, from processing step b) polyvalent alcohol there is the average functionality of 2-6, more particularly 2-4, and hydroxyl value is 50-300mgKOH/g.These structures more specifically are applicable to produce urethane, are particularly useful for flexible polyurethane foams, rigid polyurethane foam and polyurethane coating.In the production of rigid polyurethane foam and polyurethane coating, also can use the polyvalent alcohol that not yet with oxirane, carries out addition reaction in principle, in other words, based on renewable raw material and by processing step only a) and b) those polyvalent alcohols of preparing.In producing the process of flexible polyurethane foams, this compound is due to their low chain length, cause unwanted crosslinked, so be not too suitable.
Urethane is that the Aethoxy Sklerol by being prepared by the inventive method reacts production with polyisocyanates.
Urethane of the present invention be by polyisocyanates with have at least two compounds to the hydrogen atom of responding property of isocyanate groups react the preparation.In the situation that produce foam materials, reaction is carried out under the existence of whipping agent.
Initial compounds used carries out following specific evaluation:
The polyisocyanates of considering comprises conventional aliphatic series, alicyclic, araliphatic and the preferred polyfunctional isocyanate of aromatics.
Object lesson comprises: have the alkylidene group vulcabond of 4-12 carbon atom in alkylidene group, for example hexa-methylene 1, the 6-vulcabond, alicyclic diisocyanate, hexanaphthene-1 for example, 3-and-1,4-vulcabond, and any desired mixt of these isomer, hexahydrotoluene 2,4-and-2,6-vulcabond, and corresponding isomer mixture, dicyclohexyl methyl hydride 4,4 '-, 2,2 '-and 2,4 '-vulcabond, and corresponding isomer mixture, araliphatic vulcabond, for example benzene two methylene Isosorbide-5-Nitrae-vulcabond and xylylene diisocyanate isomer mixture, but vulcabond and the polyisocyanates of preferred aromatics, for example toluene 2, 4-and-2, 6-vulcabond (TDI) and corresponding isomer mixture, ditan 4, 4 '-, 2, 4 '-and 2, 2 '-vulcabond (MDI) and corresponding isomer mixture, ditan 4, 4 '-and 2, the mixture of 4 '-vulcabond, polyphenyl polymethylene polyisocyanates, ditan 4, 4 '-, 2, 4 '-and 2, the mixture of 2 '-vulcabond and polyphenyl polymethylene polyisocyanates (thick MDI), and the mixture of thick MDI and tolylene diisocyanate.Organic diisocyanate and polyisocyanates can be used separately or use with the form of mixture.
Usually, also use so-called modification polyfunctional isocyanate, these are by the product of the chemical reaction acquisition of organic diisocyanate and/or polyisocyanates.Example comprises vulcabond and/or the polyisocyanates that contains isocyanurate group and/or carbamate groups.The object lesson of considering comprises organically, the polyisocyanates that contains carbamate groups of preferred aromatics, and its NCO content is the 33-15 % by weight, preferred 31-21 % by weight, the gross weight meter based on polyisocyanates.
The polyvalent alcohol prepared by the inventive method can be used with other at least two compound combinations to the hydrogen atom of responding property of isocyanate groups that have.
At least two compounds to the hydrogen atom of responding property of isocyanate groups that have as using together with the polyvalent alcohol that can prepare with the inventive method, more specifically used Aethoxy Sklerol and/or polyesterols.
In the situation that produce rigid polyurethane foam, usually use at least one functionality at least 4 and hydroxyl value be greater than the Aethoxy Sklerol of 250mg KOH/g.
The polyesterols used together with the polyvalent alcohol prepared with the inventive method generally carries out the condensation reaction preparation by polyfunctional alcohol, the preferred diol with individual, preferred 2-6 the carbon atom of 2-12 and the polyfunctional carboxylic acids with 2-12 carbon atom, and the example of polyfunctional carboxylic acids is the naphthalic acid of succsinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, nonane diacid, sebacic acid, decane dioctyl phthalate, toxilic acid, fumaric acid and preferred phthalic acid, m-phthalic acid, terephthalic acid and isomery.
The Aethoxy Sklerol used together with the polyvalent alcohol prepared with the inventive method generally has the functionality of 2-8, more particularly 4-8.
Especially use the polyether glycol prepared by known method as polyol, for example anionoid polymerization preparation under alkali metal hydroxide exists by oxirane.
Oxirane used is ethylene oxide and 1,2-propylene oxide preferably.Oxirane can be used separately, or uses in succession, or uses as mixture.
The example of starting molecule comprises following: water, organic dicarboxylic acid, succsinic acid for example, hexanodioic acid, phthalic acid and terephthalic acid, for example in alkyl, there is the aliphatic series of 1-4 carbon atom and the optional N-monoalkyl of aromatics, N, N-and N, the diamines that N '-dialkyl group replaces, optional single-and quadrol of replacing of two-alkyl for example, diethylenetriamine, Triethylenetetramine (TETA), 1, the 3-propylene diamine, 1, 3-and/or 1, the 4-butanediamine, 1, 2-, 1, 3-, 1, 4-, 1, 5-and 1, the 6-hexamethylene-diamine, aniline, phenylenediamine, 2, 3-, 2, 4, 3, 4-and 2, the 6-tolylene diamine, and 4, 4 '-, 2, 4 '-and 2, 2 '-diaminodiphenyl-methane.
Other starting molecule comprises following: alkanolamine, for example thanomin, N-methyl-and N-ethyl-thanomin; Diethanolamine, for example diethanolamine, N-methyl-and N-ethyl-diethanolamine; Trolamine, for example trolamine; And ammonia.
Use in addition polyvalent alcohol, especially dibasic alcohol and/or trivalent alcohol, ethylene glycol, the third-1 for example, 2-and-1, the 3-glycol, glycol ether, dipropylene glycol, fourth-Isosorbide-5-Nitrae-glycol, oneself-1,6-glycol, glycerine, tetramethylolmethane, sorbyl alcohol, and sucrose; Polyphenol, for example 4,4 '-dihydroxyl ditan and 2,2-bis-(4-hydroxy phenyl) propane, resol, the Mannich condenses of for example oligomerization product of phenol and formaldehyde, and phenol, formaldehyde and diethanolamine, and melamine.
Polyether glycol has the functionality of preferred 3-8,3-6 more particularly, and hydroxyl value is preferably 120-770mg KOH/g, more particularly 240-570mg KOH/g.
There are at least two compounds to the hydrogen atom of responding property of isocyanate groups and also comprise optional common chainextender and the linking agent used.But, in order to improve mechanical property, prove and more advantageously add dual functional chainextender to have 3 or the linking agent of high functionality more, or optional their mixture.Chainextender used and/or linking agent be alkanolamine preferably, and more particularly molecular weight is less than 400, is preferably glycol and/or the triol of 60-300.
While using chainextender, linking agent or their mixture in the production at urethane, their consumption is the 0-20 % by weight normally, and preferred 2-5 % by weight, based on having at least two weighing scales to the compound of the hydrogen atom of responding property of isocyanate groups.
As whipping agent, for example can make water, it discharges carbonic acid gas while reacting with isocyanate groups.Replace water, still preferred and water is used in combination, and also can use so-called pneumatogen.These are be inertia but at room temperature be generally the compound of liquid for ingredient components, and they evaporate under the polyurethane reaction condition.The boiling point of these compounds is preferably below 100 ℃, more particularly below 80 ℃.Pneumatogen also comprises rare gas element, and they are introduced in ingredient components or are dissolved in wherein, and example is carbonic acid gas, nitrogen or rare gas.
At room temperature for the compound of liquid, usually be selected from alkane and/or the cycloalkanes with at least 4 carbon atoms, dialkyl ether, ester, ketone, acetal, have the fluoroalkane of 1-8 carbon atom, and the tetraalkyl silane, the especially tetramethylsilane that there is 1-3 carbon atom in alkyl chain.
Example comprises propane, normal butane, Trimethylmethane and tetramethylene, Skellysolve A, iso-pentane, and pentamethylene, hexanaphthene, dimethyl ether, methyl ethyl ether, methyl butyl ether, methyl-formiate, acetone, so and can in troposphere, destroy and harmless fluoroalkane, for example trifluoromethane, methylene fluoride, 1,1 to ozonosphere, 1,3,3-3-pentafluorobutane, 1,1,1,3,3-pentafluoropropane, 1,1,1,2-Tetrafluoroethane, C2H4F2 C2H4F2 and heptafluoro-propane.Described pneumatogen can be used separately or use according to any required combination with one another.
Catalyzer used more particularly can significantly accelerate those compounds that react between isocyanate groups and group to responding property of isocyanate groups.More specifically use organometallic compound, preferably have machine tin compound, for example organic acid pink salt (II).
As catalyzer, can use strong basicity amine in addition.Its example is aliphatic secondary amine, imidazoles, amidine, triazine, and alkanolamine.As required, catalyzer can be used separately or use as any required mixture each other.
Auxiliary agent used and/or auxiliary reagent are known those materials for this purpose, and example is surfactant, suds-stabilizing agent, abscess conditioning agent, filler, pigment, dyestuff, fire retardant, hydrolysis inhibitor, static inhibitor and reagent with antimycotic and antibacterial activity.
More detailed information about the initial substance for implementing the inventive method, whipping agent, catalyzer and auxiliary agent and/or auxiliary reagent can be referring to for example Kunststoffhandbuch, the 7th volume, " urethane (Polyurethane) " Carl-Hanser-Verlag Munich, the 1st edition, 1966, the 2 editions, 1983, with the 3rd edition, 1993.
With epoxidation/open loop, with hydroformylation/method for hydrogenation, compare, the advantage of the inventive method is that the ketonization operation is without any need for solvent or any catalyzer.Therefore, can obtain in more inexpensive mode fat and the derivative of fatty acid of hydroxy-functional.In addition, advantage of the present invention is: by simply choosing reaction conditions for example pressure, temperature and the residence time, can and regulate functionality according to the target mode according to very simple mode, thereby obtain the material with non-constant width range of application, even exceed the urethane range of application.
With epoxidation, with ozone decomposed, compare, the advantage that the inventive method provides is: produced oligomeric hydroxy fat, its have can freely regulated degree of hydroxylation in, no longer contain any pair of key, so no longer send out conventional weathering process lipogenous (oxidation of DB, " become and become sour ").In the situation that epoxidation and ozone decomposed, this is only in the situation that fully transform and could realize; But this depends on functionalized degree.
With hydroformylation, compare, the operation of carrying out oxidation with laughing gas allows to produce the material with complementary interaction, and this is because obtain in this case secondary hydroxyl fully, and hydroformylation reaction has produced primary hydroxyl.
Below by embodiment, the present invention is described.
Embodiment 1: use the laughing gas schou oil
The steel autoclave that is 1.2L to capacity adds the soya-bean oil of 260g, then seals and use nitrogen purging.Inject the laughing gas of 50 bar, agitator is set as to 700rpm and opens, then reaction mixture is heated to 220 ℃.After operation 22 hours, cool to room temperature, close agitator, and make autoclave slowly be reduced to environmental stress.Except after desolventizing, analyze flaxen liquid emission.
Analytical data: bromine number is 36g bromine/100g, and carbonyl value is 173mg KOH/g, and ester value is 196mgKOH/g, and acid number is 1.8mg KOH/g.Ultimate analysis: C=73.6%, H=10.8%, O=15.1%.
Embodiment 2: use the laughing gas schou oil
The steel autoclave that is 1.2L to capacity adds the soya-bean oil of 172g and the hexanaphthene of 172g, then seals and use nitrogen purging.Inject the laughing gas of 20 bar, agitator is set as to 700rpm and opens, then reaction mixture is heated to 220 ℃.After operation 36 hours, cool to room temperature, close agitator, and make autoclave slowly be reduced to environmental stress.Except after desolventizing, analyze flaxen liquid emission.
Analytical data: bromine number is 57g bromine/100g, and carbonyl value is 64mg KOH/g, and ester value is 196mgKOH/g, and acid number is 1.8mg KOH/g.Ultimate analysis: C=75.6%, H=11.5%, O=13.4%.
Embodiment 3: use the laughing gas schou oil in tubular reactor
In tubular reactor (internal volume is 210ml, and the residence time is approximately 50 minutes), under 290 ℃ and 100 bar, the 50 % by weight soya-bean oil of 130g/h and the mixture of 50 % by weight hexanaphthenes react with the laughing gas of 45g/h.To react ejecta and add in container, the liquid fraction of cooling reaction ejecta, and remove hexanaphthene by distillation.Analyze the weak yellow liquid ejecta.
Analytical data: bromine number is 54g bromine/100g, and carbonyl value is 81mg KOH/g, and ester value is 199mgKOH/g, and acid number is 2.6mg KOH/g.Ultimate analysis: C=75.0%, H=11.1%, O=13.7%.
The soya-bean oil used in all embodiments is that it has from the commodity of Aldrich company: bromine number is 80g bromine/100g, and carbonyl value is 1mg KOH/g, and saponification value is 192mg KOH/g, and acid number is<0.1mg KOH/g.Ultimate analysis shows: C=77.6%, H=11.7%, O=11.0%.
Embodiment 4: from the hydrogenation of the schou oil of embodiment 2
(carbonyl value is 64mg KOH/g from the schou oil of embodiment 2 to add 20g in the 300ml steel autoclave, hydroxyl value is<5mg KOH/1g, bromine number is 57g bromine/100g) solution in the 100ml tetrahydrofuran (THF), and add together 2g by 5% ruthenium catalyst on carbon support that loads on of water-wet.Be heated to 120 ℃, and inject the hydrogen of 120 bar.Under these parameters, stir 12 hours.Then reaction mixture is cooling and standing.Filter ejecta, and remove desolventizing by distillation.Analyze solid residue (butter shape), recording hydroxyl value is 64, carbonyl value<5, bromine number<5.
Embodiment 5: from the hydrogenation of the schou oil of embodiment 3
Add the solution of schou oil (carbonyl value=81, bromine number=54) in the 100ml tetrahydrofuran (THF) of 20g in the 300ml steel autoclave, and add together 20g by the Al that loads on of water-wet 2o 3ruthenium catalyst on carrier (0.5%).Be heated to 120 ℃, and inject the hydrogen of 100 bar.Under these parameters, stir 12 hours.Then reaction mixture is cooling and standing.Filter the reaction ejecta, then by distillation, remove desolventizing.Analyze solid residue (butter shape), recording hydroxyl value is 80, carbonyl value<5, bromine number<5.
Polyvalent alcohol from embodiment 5 is successfully used in the polyurethane coating batching.In this case, find that coating is characterised in that to have very high water-repellancy.
Embodiment 6: from the hydrogenation of the schou oil of embodiment 1
Add schou oil (carbonyl value=173, hydroxyl value<5, the bromine number=36) solution in 100ml tetrahydrofuran (THF) of 20g from embodiment 1 in the 300ml steel autoclave, and add together 2g by 5% ruthenium catalyst on carbon support that loads on of water-wet.Be heated to 120 ℃, and inject the hydrogen of 120 bar.Under these parameters, stir 12 hours.Then reaction mixture is cooling and standing.Filter ejecta, then by distillation, remove desolventizing.Analyze solid residue (butter shape), recording hydroxyl value is 170, carbonyl value<5, bromine number<5.
Polyvalent alcohol from embodiment 6 is successfully used in the rigid polyurethane foam batching.In this case, find that this system is characterised in that the consistency had between outstanding and pentane foaming agent used.

Claims (12)

1. a method for preparing polyvalent alcohol comprises the following steps:
A) unsaturated natural fat, unsaturated natural acid and/or fatty acid ester are reacted with nitrous oxide,
B) product that makes to obtain in a) in step reacts with hydrogen use heterogeneous catalyst.
2. the method for claim 1, is characterized in that unsaturated natural fat is to be selected from: Viscotrol C, raisin seed oil, Nigella damascena L. oil, Semen Cucurbitae oil, borage oil, soya-bean oil, Wheat germ oils, rapeseed oil, Trisun Oil R 80, peanut oil, Pericarppium Armeniacae Amarum oil, pistachio oil, Prunus amygdalus oil, sweet oil, Queensland nut oil, Lipoval A, Oleum Hippophae, sesame oil, cannabis oil, hazelnut oil, primrose oil, wild rose oil, Thistle oil, walnut oil, plam oil, fish oil, Oleum Cocois, Yatall MA, maize germ, linseed oil.
3. the method for claim 1, is characterized in that unsaturated natural acid and fatty acid ester are to be selected from: tetradecenoic acid, Zoomeric acid, oleic acid, vaccenic acid, petroselinic acid, gadoleic acid, erucic acid, Selacholeic acid, linolic acid, α-and gamma-linolenic acid, therapic acid, arachidonic acid, timnodonic acid, sole acid, docosahexenoic acid, and their ester.
4. the method for claim 1, is characterized in that unsaturated natural fat is to be selected from soya-bean oil, plam oil, Trisun Oil R 80, rapeseed oil and Viscotrol C.
5. the method for claim 1, it is characterized in that step a) in, nitrous oxide is used as the mixture with rare gas element.
6. the method for claim 1, is characterized in that step b) under the existence of the catalyzer that contains ruthenium, carry out.
7. the method for claim 1, is characterized in that catalyzer is applied on carrier.
8. the method for claim 1, is characterized in that carbon is used as carrier.
9. the method for claim 1, is characterized in that catalyzer is used as fixed bed.
10. according to polyvalent alcohol that in claim 1-9 prepared by any one.
11. the purposes according to the polyvalent alcohol of claim 10 for the preparation of urethane.
A 12. method for preparing urethane, wherein make polyisocyanates and there are at least two compounds to the hydrogen atom of responding property of isocyanate groups and react, it is characterized in that polyvalent alcohol according to claim 10 is as having at least two compounds to the hydrogen atom of responding property of isocyanate groups.
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